2-thienyl thionophosphine sulfide

ABSTRACT

A NOVEL COMPOUND OF 2-THIENYL THIONOPHOSPHINESFULFIDE HAVING THE FORMULA,   2,4-DI(S=),2,4-DI(THIEN-2-YL)-1,3,2,4-DITHIADIPHOSPHETANE   WHICH IS USEFUL AS ANINSECTICIDE AND A FUNGICIDE AS WELL AS AN INTERMEDIATE FOR THE PRODUCTION OF INSECTICIDES, FUNGICIDES AND THE LIKE.

3,585 212 Z-THIENYL THIONOP HOSPHINE SULFIDE Hajime Hirai, Minoo-shi,Japan, and'Hirosuke Yoshioka,

Austin, Tern, assignors to Sumitomo Chemical Company, Ltd., Osaka, JapanNo Drawing. Filed Oct. 18, 1968, Ser. No. 768,900

Claims priority, applicatligrzlipan, Oct. 31, 1967,

Int. c1. A0111 9/12; c074 63/12 U.S. Cl. zen-429p ABSTRACT OF THEDISCLOSURE A novel compound of 2-thienyl thionophosphinesulfide havingthe formula,

This invention relates to a novel compound of 2-thienylthionophosphinesulfide having the formula,

w ll

and a process for producing the same.

So far, the method for linking carbon atom and phosphorus atom ofphosphorus pentasulfide has been known, for instance in the Journal ofthe American Chemical Society, vol. 74, 4933 (1952), it is disclosed toreact cyclohexene with phosphorus penta sulfide for such long time as108 hours to prepare A -cyclohexenyl thionophosphinesulfide in 58%yield.

Further, in the said literature, vol. 78, 5018 (1956), it is alsodisclosed to react an aromatic hydrocarbon compound such as benzene,anisole and naphthalene with phosphorus penta sulfide at considerablyhigh temperature in order to complete the reaction, namely in case ofreacting anisole or naphthalene with phosphorus penta sulfide, thereaction is completed at boiling point thereof, and in case of reactingbenzene with phosphorus penta sulfide, at 225 C. in the autoclave.

While, the present inventors have found that the linkage of carbon atomand phosphorus atom can be completed easily at unexpectedly lowertemperature than that of the known method when thiophene is reacted withphosphorus penta sulfide, thereby to obtain a novel 2-thienylthionophosphinesulfide having above-mentioned formula in higher yieldcompared with said known method.

Further, the present inventors have found that the present compound canbe produced in purer state than that of the known compounds prepared bythe above-mentioned method which are, generally, so impure that thestructure thereof cannot be known without conversion to anotherderivative thereof.

A basic object of the present invention is to embody Z-thienylthionophosphinesulfide having the above-mentioned formula and anotherobject of the invention is to embody a process for producing the same.These and other objects will be apparent to those conversant with theart to which the present invention pertains from the subsequentdescription.

The objective Z-thienyl thionophosphinesulfide can be 1 Claim ice .prepared from thiophene and phosphorus penta sulfide according to thefollowing scheme:

i/ q; Tunas In carrying out the present invention, an amount ofthioprene may be not less than 2 mol. per mol. of phosphorus pentasulfide, but it is preferable that 10 to mol. of thiophene is employedin practice.

Generally speaking, decrease the amount of thiophene employed isattended with deterioration of purity of the product obtained because ofprogress of the side reaction or the polymerization reaction andincrease of the same is attended with decrease of yield per reactionvolume. The reaction can be completed within a temperature range ofbetween and 150 C., preferably under reflux.

The completion of the reaction can be confirmed by disappearance ofhydrogen sulfide from the reaction sys term. The reaction time isusually 45 to 50 hours.

After the reaction is over, separation by filtration gives yellowishgreen crystals of the objective 2-thienyl thionophosphinesulfide.

The present compound obtained may be employable for insecticide andfungicide as well as an intermediate for the production of insecticides,i.e. a novel insecticide of O- ethyl-O'-p-nitrophenyl-2-thienylphosphonothioate according to the following scheme:

O C H EXAMPLE A mixture of 320 cc. of thiophene and 44 g. of phosphoruspenta sulfide was refluxed on the oil bath at C. Appearance of hydrogensulfide was confirmed at the same time as starting of reflux and colourof the reaction mixture'turned to dark brown from yellow. After 20 hoursfrom starting of reflux, yellowish green leaflet crystals were producedfor the first time.

Disappearance of hydrogen sulfide was confirmed after 48 hoursfromstarting. The reaction mixture was cooled, and subjected to filtrationto separate crystals, which were washed with small amount of thiopheneand dried under reduced pressure. Thus, 61.5 g. of yellowish greenleaflet crystals was obtained. M.P. 205 C. (decomposed) Elementaryanalysis-Calculated (percent): C, 26.95; H, 1.69; P, 17.38. Found(percent): C, 26.41; H, 1.63; P, 17.18.

Infrared absorption (Nujol sample): 3100, 1495, 1395, 1330, 1213, 1090,1010, 860, 720, 685 cm.-

Comparative test Over a rice plants (variety: Waseasahi) grown to a 3 to4 leaves-stage in a 9 cm. (in diameter) flower pot, each 7 ml./pot ofemulsions containing test chemicals at a desired concentration adjustedwith water were individually sprayed. After two hours, a suspensioncontaining spores of Pyricularia oryzae was inoculated into the riceplants to investigate the fungicidal effects and after incubating forfive days, spots caused by the Pyricularia oryzae were observed. Theresults were as follows.

Concentration of Number of active disease spots ingredient per 10Compound (p.p.m.) leaves Present compound 1, 000 24 CZHsO O P-S CH2 1,000 28 CzHsO Control 0 106 under the trademark Kitazin.

4 What we claim is: 1. A compound of the formula,

Wi ls i JOHN D. RANDOLPH, Primary Examiner C. M. SHURKO, PrimaryExaminer US. 01. X.R. 7 424-202; 260332.5

8/1958 Chao et al. 2 60-500

